Lubricating oil and process for forming the same



April 10, 1956 A. D. ABBOTT ET AL 2,741,649

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United States Patent LUBRICATING 011. AND rnocnss son FoRMING Y rrm SAMEApplication February 19, 1953, Serial No. 337,764

14 Ciaims. (Cl. 26(i-6S3.-i)

This application relates to the provision of a novel lubricating oil anda process for producing this oil. More particularly, the inventionconcerns a process Wherein hydrocarbon waxes petroleum or other originare reacted with olefins, especially ethylene, to produce a lubricatingoil of outstanding characteristics. This application is acontinuation-in-part of our copending applications, Serial Nos. 281,446and 281,447, both filed April9, 1952, and now abandoned.

It has long been recogn zed that hydrocarbon waxes have good lubricatingqualities as long as they are maintained in the molten condition. Thus,such waxes have good lubricity, a high viscosity index, and goodstability. On the other hand, it is obvious that waxes can have but alimited utility as lubricating oils due to their high melting, or pourpoint. If this deficiency of waxes could be overcome, the resultingliquid products would receive serious consideration for many lubricatingapplications since the waxes themselves are available in a wide range ofviscosities. Accordingly, it is an object of the present invention toprovide a treatment whereby hydrocarbon waxes are so altered instructure as to efiect a major'reduction in their melting point while atthe same time preserving the desirable ubricating, stability, viscosityand viscosity index qualities of the Wax.

While attainment of the foregoing object has the efiect of providing theart with a novel lubricating oil, the synthetic oil art has nowprogressed to the point where no such oil can meet with generalcommercial acceptance unless it possesses truly outstanding and uniquecharacteristics. This is particularly the ease with synthetic oilsproposed for use as crankcase lubricants in automotive or other internalcombustion engines since such oils are considerably more costly thannatural petroleum oils and must justify the added expenditure.Experience in the field shows that a successful synthetic crankcase oil,in addition to having excellent lubricating and viscositycharacteristics, should also be fully compatible with and respond wellto treatment by, the various additives such as anti-oxidants,detergents, corrosion inhibiting agents, blooming agents, and the likewhich now are conventionally incorporated in crankcase lubricating oils.It is also important that the synthetic oil be compatible in allproportions with natural mineral oils. This is a factor of considerableimportance from the practical standpoint, for not only does it permitthe marketing of a variety of blends, each of which is particularly welladapted for a given climatic or other condition of usage, but'it alsopermits the operator of the vehicle to replenish the main body ofsynthetic oil in the crankcase with a conventional oil, if need be,without danger of forming an incompatible mixture in the crankcase.While a number of difierent synthetic oils are now available, nonefulfills all these desirable attributes, and it is therefore a furtherobject of this invention to provide from waxy hydrocarbons a novelsynthetic oil of satisfactory pour point characteristics which couplesgood lubricating, viscosity and viscosity index qualifies with a highdegree of com.-

ice

patibility with mineral oils and with the various oil additives, andwhich responds weil to treatment by said additives.

Another important quality of an automotive crankcase lubricant relatesto the amount of deposit which the oil leaves in the combustion chamberas the engine is operated. Such combustion chamber deposits, whetherattributable to the oil or to the fuel, have the efiect of increasingthe octane requirement of the engine. Due to the added costsof premiumfuels, it is desirable to keep this octane requirement increase as lowas possible even in the case of those engines having a relatively lowinitial octane requirement. The problem becomes even more serious withmany of the modern high compression engines which require the use ofpremium fuels even when the motor is clean. Accordingly, it is a highlyimportant object of this invention to provide a lubricating oil whichnot only possesses the desirable compatibility and other characteristicsoutlined above, but which also has outstandingly low deposit-formingcharacteristics when employed as the crankcase lubricant in anautomotive or other internal. combustion engine.

The nature of still other objects of this invention will appear as thedescription thereof proceeds.

We have now discovered that the foregoing objects are attained byreacting a hydrocarbon wax, or mixture of said waxes, with one or moreolefin compounds, and preferably with ethylene. This reaction, which isconducted under elevated conditions of temperature and pressure,proceeds to a certain extent even in the absence of a catalyst, thoughit-is greatly specded up and the nature of the product oil improved byusing chloroform, methylene chloride or other alkyl-halide as thecatalyst.

The oils which can be obtained in this fashionhave relativeiy low pourpoints, good lubricity and a high viscosity index. They are available ina wide range-of viscosities and hence are adapted to be employed: ascrankcase lubricants in automotive engines, as well as for otherlubricating purposes. They are compatible with mineral oils in allproportions and at any desired temperature, and blends of outstandingquality have been prepared. They are also fully compatible, whenemployed either alone or in a mineral oil blend, with the various oiladditives, and they respond well to treatment by said additives. Inthese as well as other particulars, the present oils are far superior toother types of synthetic oils which are presently available on themarket.

The oils of the present invention are also characterized by abnormallylow deposit-forming characteristics when employed as crankcaselubricants in internal combustion engines. In consequence, the use ofsaid oils (or of ineral oil blendsv containing substantial amounts ofthe present oils) in a clean engine has the effect of establishing alower ultimate octane requirement than is the case when a conventionalmineral oil is employed alone, the same fuel being used in both cases.While the present oils thus make for improved engine performance byreducing engine. deposits, it should also be noted that the highviscosity index of these oils makes it possible to employ a much light rgrade thereof than would otherwise be practical and thereby efiect asignificant reduction in frictional losses as compared with thoseexperienced when a heavier-grade of oil is used. Any such reduction infrictional loss is accompanied by a corresponding increase in themileage obtained with any given fuel.

The waxy compound, or mixture or" such compounds, to be reacted with theolefin can be any hydrocarbon of predominantly open-chain configurationwhich contains from about 15 to carbon atoms in the molecule, and whichis substantially free of aliphatic unsaturation. Included are variousmembers of the parafiin series of hydro: carbons such as pentadecane,hexadecane (cetane'), 2-

methylheptadecane, 4-propylnonadecane, eicosane, pentacosane,octacosane, triacontane, tritetracontane, heptaconcane and the like, aswell as hydrocarbon compounds Containing a long hydrocarbon chain suchas dodecyl cyclohexane, octadecylbenzene, 2-octadecyldecalin, andtetradecylcyclopentane. Also included are various erystalline andmicro-crystalline .parafiin waxes, including slack and petrolatum waxesand wax mixtures, ceresin, o'zokarite and polyethylene waxes as well asthose derived from the Fischer-Tropsch synthesis or by the destructiveor non-destructive hydrogenation of synthetichydrocarbons, coal,'shaleoil or the like. These waxes, many of which are made up of a mixture ofvarious hydrocarbon compounds and which frequently contain smallpercentages of other, non-paraffinic compounds such'as naphthenes andthe like, can be employed either in the form in which they arerecovered, or they can first be separated into particular compounds,fractions, or mixtures of such compounds or fractions, with theseparated component(s) then being reacted with olefin to form the oilsof the present invention. Of the available hydrocarbon wax reactants, 'apreferred class for the purpose of this invention is made up of thevarious crystalline and micro-crystalline waves which are recovered frompetroleum oils; these parafiin waxes consist essentially of saturated,open-chain petroleum refining processes, and such mixtures can beemployed directly, if desired. Ethylene, whether employed alone or asthe principal constituent of a gaseous mixture, constitutes the mostpreferred olefinic reactant. Otherexarnples of olefinic reactants whichcan be' employed in this invention are pentene-l; pentene-2; 2-'r'nethylbutene-l; cyclopentene, cyclohexene, 3-methylbutene-l;2-methylbutene-2; hexene-l; 3-methylpentene- 2; heptene-l; octene-l;octene-2; decene-l; and decene-2.

' 'As indicated above, the present reaction proceeds in the mostfavorable manner in the presence of a catalyst, and a suitable materialof this class is therefore preferably employed. The only compounds whichhave been demonstrated to have a beneficial catalytic action in theprocessor this invention are the hydrocarbyl halides, and moreparticularly the alkyl halides. Included within this term are suchcompounds as chloroform, methylene chloride, methyl chloride, carbontetrachloride, tetrachloroethane, 'dichloropropane, butyl chloride,chlorinated naphthas, methylene fluoride, propyl bromide, octyl iodide,dichlo ro-monofiuoromethane, and the like.

' In "carrying out the reaction of olefin and wax, there is-employedfrom about 1 to 25 moles of the olefin per mole of wax. A preferredreactant ratio, however, is from about 2 to 10 moles of olefin per moleof wax. The amount of catalyst to be employed will vary somewhatdepending on the nature of the reactants, as well as upon the particularcatalyst material, or mixture of said ma terials, which is used. Ingeneral, good results have been obtained by using from 0.1 to 10% byweight of the catalyst, while a preferred range is from 1 to 5% byweight,- both of these percentages being based on the Weight of waxcharged.

The reaction'of the present invention is carried out, under the elevatedconditions of temperature and pressure discussed below, by bringing theolefin into reactive en gagement with the Wax reactant as the latter ismaintained in the liquid condition; as aforesaid, a catalyst ispreferably present in the reaction mixture also. The wax may be placedin the liquid condition by melting the same or their high pour points.The Minas and Ute Tribal .grudes,

having pour points in some instances as high as .F., are exemplary ofsuch products. These crudes, or waxcontaining distillates or residuesobtained therefrom, can be reacted with an olefin in accordance with theprocess of this invention, with the result that a substantial por- 'tionof the wax present therein is converted to a lubricat ing oil of lowpour point. This not only improves the yield of lubricating oil from thestarting material, but also so decreases the pour point of said materialas to greatly facilitate the handling and refining thereof, When thisprocedure is adopted, the wax-olefin oil produced is .nor mally leftwith the other oil as the resulting oil blend has excellent over-allproperties. v

The reaction between the olefin and the wax proceeds at temperatures offrom about 400 to about 700 F. Superatmospheric pressures are employed,primarily) to promote the solution of the olefin reactant in the liquidWax material and to maintain the other components of the system in aliquid condition at the elevated temperatures employed. While anypressure between about and 15,000 p. s. i. g. can be employed, pressuresbetween about 1,000 and 4,000 p. s. i. g. are preferred. This presethaneor other inert gases can also be employed for this purpose. In suchcases, the olefin can be supplied in liquid form, if desired, whenphysically possible. 7

In carrying out the process of this invention, a number of competingreactions take place, and it is thought that a proper understanding ofthese reactions is essential to an intelligent expression of thepreferred reaction condiditions and operating procedures to be employed.The predominant reaction is believed to be one wherein the wax isalkylated by the olefin; thus, in the case of ethylene, a given waxmolecule would acquire at least one, and usually more than one, ethylside chain; Polymerization of the olefin reactant also plays asignificant, though minor 1 role in the reaction, while a third reaction(which normally takes place in very small degree) involves the crackingof the waxy starting material or the alkylated wax product. The crackingreaction is a particularly deleterious one, for if it occurs to anyappreciable extent the deposit-forming and additive-responsive qualitiesof the final oil product are seriously impaired. Fortunately, it has nowbeen found that the cracking reaction can be substantially eliminated bymaintaining the reaction temperature below about 700 F.Whiletemperatures between 700 and 800 F. would otherwise be desirablesince they have the effect of speeding up the desired alkylationreaction, such temperatures cannot be employed for more than relativelyshort periods of time if cracking of the wax is to be avoided. On theother hand, temperaturesabove 600 FL are preferably employed Whereverpossible so as to speed the reaction as much as possible withoutotherwise adversely afiecting the course thereof. The olefin polymeriz'ation reaction is also undesirable, though to a lesser extent thanis the case with the cracking reaction. We have found that the olefinpolymerization reaction can be minimized by gradually adding the olefinto the heated Wax as the reaction progresses, the addition of olefinbeing made in a continuous or intermittent fashion, as more particularlydescribed below. Accordingly, in the preferred practice of thisinvention, reaction temperatures between 600 and 700 F. are employed,and the olefin is'added to the heated reaction mixture (preferably alongwith catalyst) as the reaction progresses. M As indicated above, thereaction time will vary depending on the temperature employed. It alsovaries with the nature ofthe olefin,reactant and the relative rate atwhich. the olefin is admitted to the reaction zone, Thus, ethylene ismuch more reactive than the other olefins and requires a shorterreaction period. As a general rule, however, good results are obtainedusing reaction periods of from 1 to 20 hours, and in some cases,appreciable reaction will occur in even shorter periods, particularlywith ethylene.

a As will occur to those skilled in the art, the reaction may be carriedout batchwise, as in an autoclave, semi- I continuously or continuously,as in a tube reactor. The

olefin, moreover, may be charged to the reaction zone all at onetime orin portions. The pressure in the reaction zone may be maintained'by theolefin alone or, as indicated above, an inert gas may be used in aidingmaintenance of the desired pressure. The reaction is essentially aliquid phase reaction; that is, reaction occurs between liquid wax andolefin dissolved therein. Accordingly, agitation of the reaction mixturewill be found advantageous. Moreover, it is often desirable to avoid toohigh a concentration of olefin in order to discourage competingreactions, such as the polymerization of the olefin. Therefore, in orderto encourage the preferential reaction of addition of olefin to wax andto ensure a more uniform distribution of olefin on the wax molecules,the olefin preferably is gradually charged to the reaction zone as thereaction progresses. In operating batchwise, this can conveniently beaccomplished by adding the olefin to .the reaction vessel in successiveincrements, each of the order of about 5 to 40 per cent of the totalolefin charge. After all of the olefin has been added (either with orwithout an inert gas employed to maintain the desired pressure),reaction is deemed complete in batchwise operations when the drop inpressure substantially ceases. When operating in a continuous, orsemicontinuous fashion,'a small amount'of olefin under suitable pressuremay continuously be added'to the reaction mixture, or wax and olefin mayboth be continuously supplied to a suitable reaction zone, with thereaction mixture also being continuously withdrawn from said zone.

Once the reaction between the olefin and wax is complete, the resultingwax-olefin oil can then be separated from the other components of thereaction mixture by a practice of conventional refining techniques asmore particularly described below in connection with the drawing.Briefly, however, the separation process normally involves a preliminarydistillation to free the mixture of lighter ends (preferably thoseboiling below 250 F. at 1 mm. Hg) and thereby recover a light oil whichis essentially comprised of. polymerized olefin reactant. This isfollowed by a dewaxing step to remove unreacted waxes. Depending on theseverity of the dewaxing treatment, oils are recovered having pourpoints of from below -6S F. to F. The resulting dewaxed oil productshave viscosities which are much'the same as those of the molten waxystarting materials, and vary from about 33 to 80 or more SSU at 210 F.The viscosity index of the present oils normally is well in excess of100 and preferably 'is 130 or more, except as lowered by the use of ablending oil. 0

.The oil of this invention (apart from any blend thereof with mineraloil) is essentially comprised of the waxolefin alkylation productresulting from the reaction of the wax with the olefin, this productnormally comprising from about 60 to 95 by weight of the oil. Thebalance of the oil is madeup essentially of polymerized olefin reactant.Therelative amount of this component which is presentdepends upon theconditions which were employed in forming the oil, and particularly onwhether or not said conditions favored polymerization of the olefins aswell as on the severity of the distillation procedures practiced inrecovering the oil from the crude reaction mixture. Thus, if desired,the wax-olefin oil of this invention can be obtained in a formsubstantially free of any polyolefin component by first carefullyminimizing the amount of said polymer formed during the alkylation step,and by then subjecting the oil, either before or after the dewaxingstep, to a distillation treatment which is rigorous enough to remove themore volatile olefin polymer. Inasmuch as distillation treatments ofthis character normally lead to serious losses of the wax-olefinalkylate, and since excellent results are obtained with oils containingeven relatively large amounts of the polymer, the preferred practice isto obtain as final product an oil which contains from to 90% of thewax-olefin alkylate and from 10 to 30% of the olefin polymer. The oilswill also contain a small percentage (usually varying from a fraction ofa percentup to about 4 or 5%) of various other materials such asunreacted waxes, partially cracked waxes, and the like. However, thesematerials make no particular contribution to the properties of the oiland may be regarded as impurities. They therefore have been disregardedin the foregoing statement of the preferred oil composition.

Reference is now made to the accompanying drawing which illustratesdiagrammatically a process for carrying out one embodiment of theinvention. According to this embodiment of the invention, olefin and Waxare charged to a reactor, such as the coil reactor described in Example1, either directly or into a mixing line or zone leading into thereactor. After reaction, the reaction products are introduced into a gasseparation zone, wherein the light gases are separated from the heavierliquid fractions. Part or all of these light gases may then be bled offthe system; or part or all of these gases may be recycled for use asolefins, preferably after treatment in an olefin concentration zoneinvolving fractionation, adsorption or absorption, as is known in theart. The heavier liquid fraction from the gas separation zone isintroduced into a distillation zone of one or more stills wherein afurther separation light and heavy fractions is effected, the lightfraction being recycled or bled oif and the heavier fraction, dewaxed togive the Wax-olefin oil of this invention. This wax, which may vary inamount from about 10 to (in terms of the weight of wax charged)depending on the relative amount of olefin employed and the over-allseverity of the reaction, is then available for further reaction withthe olefin.

Referring to the drawing, the numeral 2 indicates a Wax storage vesselor tank equipped with heating means, such as coil 3, to render ormaintain the wax fluid. The numeral 4 indicates storage vessel or tankfor olefins, which may be introduced thereinto through valved line5,-from an outside source, not shown. Fluid wax from storage tank 2 isintroduced through line 7 into reactor 9-, while olefin material, forexample, ethylene, is introduced thereinto through line 8. c

After reaction is complete, the reaction products are introduced throughline 10 into gas separator 11. Light fraction or gases are removed fromthe gas separator through line 12. Part or all of these gases may bebled 03 through valved line 13 or part or all recycled to olefin storage4 through line 14. Overhead from gas separator 13 can be charged throughline 15 to olefinconcentrator 16, wherein the olefins are concentrated,and then recycled through liues 17 and 14 to olefin storage, thesaturated, or reject fraction being removed through line 18. The heavierfractions from gas separator 11 are charged through line 19 to still 20to eifect a further separation of lighter and heavier fractions.Thelight fractions from still 20 are removed through line 21, and partor all bled off through line 22 or part or all recycled through line 14to olefin storage 4. The heavier waxy oil fraction from still 2il ischarged through line 23 to dewaxer 24 to obtain a low pour point oilthrough line 25, and also-wax, which may be recycled to wax storagethrough line 26. The oil from line 25 may, if desired, be subjected tofurther distillation treatment to separate the oil into relatively lightand heavy grades. 7

The oil of the present invention is well adapted to be asthe initiallyclean engine was run using a commercial isooctanc fuel."

TheLauson engine was operated continuously for 240 hrs. at 'full'throttle'('1200R.' P. M.) using a 15 spark advance, a'jacket temperatureof 210 F., a sump temperature of 150 F. and an air/fuel ratio ofapproximately 14:1 by weight. At the end of this period the octanerequirement had increased by only 22 research numbers when theWax-olefin oil of this invention was used. In a companion test conductedunder the same circumstances, but with a highly refined, wax-free baseoil of'SAESO grade having viscosity index of 85 and derivednonrcaliforniawaxy crude, the octane increase was'43"rese'arcnnuniberst'Theoldsmebile'enginewas operated for a continuous period of"'240"hours'at"2000'R. P. M.', with 35 spark advance, 'aloa'dof 16 brake horsepower,a jacket temperature of 180 F., and a sump temperature of 165 F. Herethe octane requirement increased was 5 research numbers with thewax-olefin oil and 14 research numbers with the mineral oil as definedin the foregoing paragraph.

EXAMPLE 4 In this example a micro-crystalline wax mixture obtained frompetroleum oil and melting above 175 F.

which had a viscosity of 80 SSU at 210 and an estimated viscosity indexof 122 was employed. In carrying out the operation 600 gms. of the waxwere charged to a pressure bomb and heated to 665 F To the bomb was thencharged 150 gms. of ethylene and 10 gms. of chloroform, the pressure inthe bomb then being 1650 p. s. i. g. The bomb was then heated for aperiod of 74 minutes at a temperature of about 670 F., after which afurther increment of 100 gms. of ethylene and 5 gms. of chloroform wereadded. The heating was then continued for a fur- (her period of 127minutes, the pressure in the bomb being 1250 p. s. i. g. at the end ofthis second heating period. On releasing the gas from the bomb there wasrecovered 710 gms. of liquid product. 118 gms. of this product were thentopped to remove the portion (5.3 gms.) boiling below 395 F. (pottemperature) at 1 mm. Hg. The remainder of the liquid product was thensolvent dewaxed at 20 F., whereby there was recovered 55.3 gms. of awax-olefin oil having a pour point of F., a viscosity of 63.2 SSU at 210F. and a viscosityindex of 135.

7 EXAMPLE About 400 gms. of AMP 125-130 'wax (molecular weight about375), 215 gms. of ethylene and 10 gms. of chloroform were charged to abomb. The pressure in the bomb was then 1000 p. s. i. g. -The bomb washeated to a temperature of about 640 F. overa period-of 12 hours and wasthen held at this temperature for 5% hours, the pressure being 1600 p.s. i. g. as the bomb reached 194 F., 3290 p. s. i. g. at a bombtemperature of 507 F., and 1600p. s.- i. g. as the final temperature of640 F. was reached. At the end of the.'5%'-h0l.ll-h63ting, the pressurein the bomb had dropped to 650 p. s'. i. g. On releasing the gaspressure within the bomb, there was recovered 586 gms. of liquidreaction mixture which was then distilled to remove the portion boilingbelow 330 F. at 2.5 mm. Hg. The heavier oil recovered was then solventdewaxed at -15 F., thereby yielding 401 gms. of oil having a pour pointof 5 F., a viscosity of 41.5 SSU at 210 F., and a viscosity index of143.. When this oil was more severely dewaxed (at -50 1 there wasrecovered 369 gms. of 'oil having a pour point of R, a viscosity of 41.5SSU at 210 F.- and a viscosity index of 139.

EXAMPLE'6 The wax-olefin oil having the 35 F. pour point, whosepreparation is described in the previous example, was blended with aneutral mineral oil which was'a solvent refined, California paraflinbase oil having a viscosity of 150 SSU- at 100 1 a viscosity index of'87 and apour' point of ---5 F., blends being prepared containingbetween 10% "of the wax-olefin oil and of the mineral oil-to 90% of thewaxolefin oil and'10% of the mineraloilu-Th'e'se blends were miscible atall temperatures down to the pour point of the particular blendinvolved. Forthe sake of comparison, blends were made of the samemineral oil with a conventional synthetic oil of the polyglycol type,the particularpolyglyc'ol chosen being a" methyl phenyl diether ofpolypropylene glycol having a molecular weight of about 1000. The blendsso prepared were miscible only at relatively elevated temperatures;thus, a blend comprising 60% of mineral oil and 40% of thepolyglycol wasmiscible only at'temperatures above 72 F. When the mineral oil wasblended with an equal amount of a synthetic oil comprising a methyl sec.butyl diether of polypropylene glycol having a molecular weight of about500,'it was found that "the blend was compatible only at temperaturesabove 18' In another seriesof-tests the wax-olefin oil referred to abovewas blended with various of the additives" which are customarilyemployed in lubricating oils. In one such test the oil was found to becompatible with a total of at least millimoles of a calcium petroleumsulfonate and sulfurized calcium phenate per kg. of oil, the phenatenormally being used in the proportion of approximately 2 moles for eachmole of the sulfonate. On the other-hand, it was found that amounts'assmall as 5 millim'oles of said additives per kg; of oil wouldprecipitate out'at room temperature'from a conventional polyglycol oil,here a monooctyl ether of polyglycol acetate having a molecularweight'of about 500.

I It vas'also obs'ervedtha't the additive-containing'waxolefin' oilswere not compatiblewith water and that even agitation of the compou'ndedoil'"with water did notaffeet the composition. On the other hand, thepolygl-ycol compositions were found to be readily compatible with waterand the" presence ofas little as 0.2% by weight of Water therein had theeffect of causing the immediate decomposition, and precipitation fromthe mixture, of the phenate additive. W

EXAMPLE 7 In this operation 100'parts of commercial eicosane,whichcontained .6 parts of oil having a 0 pour point, were reacted in apressure vessel with 45 parts of ethylene for. avperiod of one hour atan average temperature of about 670 F., the pressure. at the beginningof the reaction being 2650p. s. 'i. :g. andjat the end of the reaction,1600p. s..i. g. On distilling off the portion of thereaction mixtureboiling below 250 F. at 1 Hg and then solventdewaxing'the remainingliquid at -20 F"., there was recovered 31.3 parts of a heavy oil havinga pout-"point of 0 E, a vis of 37 SSU at 210" F., and a viscosity indexof about 130. Whenfthe foregoing. run wasrepeated, but with the additionof 2 parts "of chloro form as catalyst, the yield of heavy oil of 0"pour point was increased to 51.4 parts. In each of these reactions,there was recovered approximately 29 parts of unreacted ethylene. V

The runs described in the preceding paragraph were thenrep'eate d, using2-hour and 4-hour reaction periods, respectively. Witlf tlie use ofchloroform 'catalySt' the amount of heavy oil recovered was 60 and 85.5parts at 2 and 4 hours respectively, while in the uncatalyzed runs theincreasein the yield of heavy oil was such as to yield 34.4 parts and42.4 parts as reaction periods of 2 and 4 hours were employed. 7 V VAgain repeating the forcgoing runs with catalyst, but at 620 F., itwasfound that the 2- and 4-hour reaction periods resulted in the productionof 41 and 53.6 parts, respectively," of heavy dilof 0 F. pour point.

EXAMPLE 8 This operation was conducted by employing thezsame reactionconditions as described in thefirst paragraph action period to 4 hourshad the effect of increasing the yield of heavy oil to about 26 parts(in the absence of catalyst) and to about 45 parts with the employmentof 2.4 parts of chloroform catalyst.

EXAMPLE 9 In this example eicosane was subjected to reaction first aloneand then in the'presence of ethane and chloroform The first reactioninvolved heating 100 parts of eicosane, in a suitable pressure vessel,to 662 F. and maintaining the contents of the vessel at that temperaturefor 5 hours. On distilling the resulting product in vacuo to obtain alight oil fraction, and then solvent dewaxing the higher boilingmaterials at F., there was obtained a total of but 7.2 parts of bothlight oil and the heavier 0 F. pour point material. Since the eicosanestarting material (which was of commercial grade) contained 6 parts of 0F. pour point oil, this is evidence that substantially no reactionoccurred during the heating of the eicosane.

To determine whether the presence of a catalyst would have any effect-onthe reactivity of eicosane in the absence of any olefinic reactant,though under elevated pressure conditions, 300 parts of commercialeicosane were heated to 660 F. At this point the pressure vessel wascharged with 134 parts of ethane and 6 parts of chloro-.

.form. The .vessel, at an initial pressure of 2100 p. s. i. g.,

was now heatedfor 2 hours at 660 F. At the end of this time the pressurein the vessel was still 2100 p. s. i. g. The liquid product was thenworked up by topping oif a small amount of a light oil and by thensolvent dewaxing.

the residue at -20 F. Here again, however, as in the operation describedin the preceding paragraph, the total amount of light and heavy oilsrecovered did not appreciably exceed that contained in the eicosanestarting material.

' EXAMPLE 10 This operation was conducted to compare the eflicacy of anumber of different catalysts. The procedure employed with each catalystwas to react 300 parts of commercial eicosane with approximately 150parts of ethylene at a temperature of about 670 F. for a period of 4hours. The resulting liquid reaction mixtures were treated by topping toremove the lighter oil fraction boiling below about 250 F. at 1 mm. Hgand by then solvent dewaxing the residue at '-20 F. to determine theamount of 0 F. pour point oil produced during the reaction. In the tablebelow, which lists the catalyst employed, the amount of 0F. pour pointoil is expressed in terms of parts per 100 parts of the eicosanestarting material employed.

Table I I Amt. of 0 F.

Catalyst Pour Point Z1101: (7 parts)-.. BF; (7 parts)..--

300 parts of wax (M.P.=125-130 F., M. W.=375), 300 parts of 2-butene and6 parts of chloroform were Oil Produced 12 a charged to a bomb. The bombwas heated to about 670 F. over a period of 5 hours and held at thistemperature for an additional period of 8 hours. A yield of 465 parts ofliquid product was obtained which after distillation to remove lightoverhead left 443 parts of heavy oil boiling above 365 F. at 4 mm. ofmercury pressure. This oil was dewaxed at 55 F. using methyl isobutylketone as a solvent yielding 88 parts of oil having the followingproperties:

Viscosity, centistokes:

0 F 662.5 100 F 19.6 130F 11.34 210 F 4.06 Viscosity index 122 Pourpoint, F. -20

EXAMPLE 12 814 parts Minas crude oil,'425 parts ethylene and 19 partschloroform were charged to a bomb and heated at a temperature of about650 F. for 10 hours.

A yield of 993.6 parts of liquid product was obtained after reaction. Acomparison of the properties of this liquid with those of the originalcrude oil are as follows:

Original I Treated Property Crude Crude Gravity, API 35.8 37.2 PourPoint, F +.5 Below -60 Fraction boiling above 430 F. at 1 mm. Hg:

Oil, percent 17.6 26.2 Wax, percent 20.2 i .8 Asphaltenes, percent 2.00. 2 Resins, percent. 8. 4 5. 9

These data show that the lubricating oil content was 'materiallyincreased by the treatment with ethylene at the expense of the wax,asphaltenes and resins.

A comparison of the properties of the lubricating oil before and aftertreatment follows:

Original 7 Treated Crude Crude Viscosity at 100 F. ssU 1110 955. 4Viscosity at 210 F. SSU.. 82.1 86. 0 Viscosity Index V 68 EXAMPLE 13 Inmany cases it is advantageous to remove the un- Hydro- Unhydro-Properties genated Oil genated Oil Gravity, API 38. 3 38.1 BromineNumber.... 2 12 Pour Point, F 20 10 Viscosity. eentistokes:

210 F 4.6 4.7 130 F... 12.8 13.1 22. 2 22. 6 Viscosity Index 143 '15Induction Period, Hours 3. 3 2. 2

1 Both oils compounded with 0.1% phenyl-a-naphthylamine. and theinduction period, a criterion of oxidative stability, determined inaccordance with the procedure and apparatus describedinIndustrial andEngineering Chemistry, vol. 28, p. 26 (1936).

13 EXAMPLE 14 Gravity, API 38.9 Bromine number 17 Molecular weight 360Viscosity, centistokes:

100 F. 13.68 130 F. 8.27 210 F. 3.23 Viscosity index 115 EXAMPLE 15 To abomb there were charged 554 parts of cetane, 425 parts of ethylene and23 parts of chloroform. The bomb was heated to a temperature of about650 F, over a period of 8 hours and then kept at a temperature of about640 F. for 8 hours. After reaction, 910 parts of liquid reactionproducts were obtained. This mixture was distilled to a temperature ofabout 270 F. at 2.7 mm. of mercury pressure to remove unreacted ceta'ne.A yield of 639 parts of product boiling above cetane was then isolated.This liquid was subjected to dewaxing at -50 F. using methyl isobutylketone as the solvent. The yield of dewaxed oil was 248 parts. The oilhad a molecular weight of 305, and a pour point of 45 F.

While the oils of the present invention find particular utility ascrankcase lubricants in automotive and other types of internalcombustion engines, they are also useful as torque or power transmittingfluids and as lubricants for many specialized applications, includingthe lubrication of gas turbines, gears, and aircraft engines. Thelubricating oils of this invention may also be used advantageously asbase oils for grease compositions. That is, the oils herein may bethickened to the consistency of greases by incorporating therein suchthickening agents as metal soaps (e. g., calcium stearate, lithiumhydroxy stearate, etc.), polymers of ethylene (i. e., linear solidethylene polymers), inorganic aerogels (e. g., silica, thoria, etc.),polymeric nitrogen-containing compounds (e. g., polyamides obtained fromamines and dibasic acids), and the like.

The utility of the present oils for many of the above purposes,particularly those relating to the use of said oils as gas turbinelubricants or as aviation oils or greases, is largely attributable tothe fact that the slope of the viscosity curve of these oils decreases,or takes a downward turn, at lower temperatures, notably those which arewell below F. Thus, an oil derived by reacting eicosane with ethyleneand which has a viscosity of 2.85 centistokes at 210 F. and of 11centistokes at 100 F. and would, by extrapolation, be calculated to havea viscosity of 10,000 centistokes at 65 F., actually proves to have aviscosity of but 7,600 centistokes at 65" F.

Unless otherwise indicated herein, the parts or percentages given are ona weight basis.

We claim:

1. In a process for converting a normally solid hydrocarbon wax to alubricating oil, the steps comprising reacting said wax with an olefinof from 2 to carbon atoms in the presence of a hydrocarbyl halidecatalyst at a temperature between 400 and 700 F. and at a pressurebetween and 15,000 p. i. g.; and separating from the resulting reactionmixture the constituents boiling below 250 F. at 1 mm. Hg as well as theunreacted wax; the residual oil obtained in this fashion beingcharacterized by a viscosity index of at least 100 and by a pour pointnot greater than about 10 F.

2. A lubricating oil produced by the method of claim 1.

3. The process of claim 1, wherein the olefin reactant is ethylene andthe catalyst is an alkyl halide.

4. The process of claim 1, wherein the wax reactant is a hydrocarbon ofpredominantly open-chain configuration which contains from about 15 to100 carbon atoms in the molecule, the olefin reactant is ethylene, andthe catalyst is an alkyl halide.

5. In a process for converting a normally solid hydrocarbon wax to alubricating oil, the steps comprising bringing said wax into reactiveengagement with ethylene in the presence of a chloroform catalyst atsuperatmospheric pressure and at a temperature between 600 and 700 F.,said reactants being employed in the proportion of from 1 to 25 moles ofethylene per mole of wax; distilling the lighter ends from the resultingreaction mixture; and treating the remaining heavy residue to removeunreacted wax therefrom; the resulting liquid oil product beingcharacterized by a viscosity index of at least 100 and by a pour pointnot greater than about 10 F.

6. The process of claim 5 wherein the wax reactant is a parafiinichydrocarbon containing from about 20 to 40 carbon atoms in the molecule.

7. The process of claim 5 wherein the Wax reactant is eicosane.

8. In a process for producing a lubricating oil, the steps comprisingreacting at least one normally gaseous olefin with a mixture of paraifinwaxes of petroleum origin in the presence of an alkyl halide catalyst,said reaction being conducted at a temperature between about 600 andabout 700 F. and at a superatmospheric pressure, and said reactantsbeing employed in the ratio of from about 1 to 25 moles of the olefinfor each mole of wax; and then isolating from the reaction mixture soobtained a lubricating oil having a viscosity index of at least 100 anda pour point not greater than about 10 F.

9. A lubricating oil produced by the method of claim 8.

10. The process of claim 8 wherein the olefin reactant is comprisedpredominantly of ethylene.

11. The process of claim 10, wherein the catalyst is chloroform.

12. The process of claim 10, wherein the catalyst is methylene chloride.

13. In a method for lowering the pour point of a waxbearing materialselected from the group consisting of waxbearing crude oils,distillation and lubricating oils, the steps comprising reacting saidwax-bearing material with at least one olefin of from 2 to 10 carbonatoms in the presence of an alkyl halide catalyst, said reactants beingemployed in the ratio of from 1 to 25 moles of said olefin for each moleof wax present in the waxy starting material, and said reaction beingconducted at a temperature between 400 and 700 F. and undersuperatmospheric pressure.

14. The product produced by the method of claim 13.

References Cited in the file of this patent UNITED STATES PATENTS2,063,623 Pier et a1. Dec. 8, 1936 2,410,107 Sachanen et a1. Oct. 29,1946

1. IN A PROCESS FOR CONVERTING A NORMALLY SOLID HYDROCARBON WAX TO ALUBRICATING OIL, THE STEPS COMPRISING REACTING SAID WAX WITH AN OLEFINOF FROM
 2. TO 10 CARBON ATOMS IN THE PRESENCE OF A HYDROCARBYL HALIDECATALYST AT A TEMPERATURE BETWEEN 400 AND 700* F. AND AT A PRESSUREBETWEEN 100 AND 15,000 P. S. I. G,; AND SEPARATING FROM